CN104746236A - Polyimide/polyethylene oxide cable type composite nanometer fiber membrane and preparation method thereof - Google Patents
Polyimide/polyethylene oxide cable type composite nanometer fiber membrane and preparation method thereof Download PDFInfo
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- CN104746236A CN104746236A CN201310726479.2A CN201310726479A CN104746236A CN 104746236 A CN104746236 A CN 104746236A CN 201310726479 A CN201310726479 A CN 201310726479A CN 104746236 A CN104746236 A CN 104746236A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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Abstract
The invention discloses a polyimide/polyethylene oxide cable type composite nanometer fiber membrane and a preparation method thereof. The polyimide/polyethylene oxide cable type composite nanometer fiber membrane is formed by cable type composite nanometer fibers which contain polyimide core layers and polyethylene oxide surface layers. Polyethylene oxide is used as the shell layers and wraps the outer layers of polyimide, and therefore the polyimide/polyethylene oxide cable type composite nanometer fiber membrane not only has excellent properties of mechanical performance, high temperature stability and the like of the polyimide, but also has the advantages of the polyethylene oxide of being strong in liquid imbibitions and retention ability and high in electric conductivity, and is a promising gel polymer electrolyte used in a lithium ion battery.
Description
Technical field
The present invention relates to a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane and preparation method thereof, particularly, the present invention relates to a kind of coaxial electrostatic spinning technology that adopts and prepare polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane that can be used for lithium ion battery and preparation method thereof.
Background technology
Method of electrostatic spinning is a kind of important method preparing superfine fibre, and as far back as 1934, Formhals just described the technology utilizing electrostatic repulsion to obtain polymer filaments first in U.S. Patent application 1975504 [P].In recent years, along with the development of nanosecond science and technology, this technology obtains the extensive concern of people again.The appearance of coaxial electrostatic spinning technology can be described as the result further furtherd investigate electrostatic spinning technique.
Coaxial electrostatic spinning technology prepares the process of fiber: immiscible two kinds of spinning solutions are placed in inside and outside syringe respectively, and under electric field force effect, the polymeric liquid of spinning nozzle capillary tip forms coaxial Taylor and bores.When field intensity reach several thousand even several ten thousand volts time, charged liquid overcomes its surface tension and forms coaxial jet.Along with solvent evaporates, jet solidification, on the receiving screen of band opposite electrode, form superfine fibre film.Under certain condition, by electrostatic repulsion, Coulomb force and capillary acting in conjunction, polymer jet can along the helical trajectory bending motion of instability, drafted thousands of times within a few tens of milliseconds, thus forms submicron order to the coaxial fiber of nano level superfine.
In recent years, coaxial electrostatic spinning technology is utilized to prepare the document of composite nano fiber and patent application has a lot, such as: at document [Tao Song et al.Chemical Physics Letters [J], 2005,415:317] in, Song etc. adopt coaxial electrostatic spinning technology to prepare FePt magnetic particle/PCL coaxial nano cable.In patent application CN103088442A, execute the people such as beautiful monarch disclose the method adopting coaxial electrostatic spinning technology to prepare doughnut.In patent application CN103102067A, the people such as Liu Li discloses a kind of coaxial electrostatic spinning technology that adopts and prepares rough surface SiO
2the method of fiber.In patent application CN101509153, the people such as elegant plum does not disclose a kind of method adopting coaxial electrostatic spinning technology to prepare shell-core structure medicament nano-fibre.
Wherein, in patent application CN102230257A, disclose a kind of coaxial compound nanometre fibre film and preparation method's application, what adopt in the disclosure in this patent is fluoropolymer, there is the defects such as pollution.
Therefore, the further research that how to provide a kind of new green environment protection pollution-free and the cable-type composite nano-fiber membrane that electrical conductivity is high needs and urgently developing.
Summary of the invention
The object of the invention is to the cable-type composite nano-fiber membrane for lithium ion battery of the prior art have and fluorine-containingly wait poisonous polymers and the low shortcoming of electrical conductivity, provide a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane and preparation method thereof.
The invention provides a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein, this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is formed by the cable-type composite nano fiber containing polyimides sandwich layer and polyethylene glycol oxide cortex.
Present invention also offers the preparation method of a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein, the method comprises the following steps:
(1) polyamic acid/polyethylene glycol oxide cable-type composite nano fiber polyamic acid solution as inner fluid and the polyethylene oxide solutions as outer fluid prepared by coaxial electrostatic spinning silk device, and the polyamic acid of preparation/polyethylene glycol oxide cable-type composite nano fiber is collected on dull and stereotyped wire drawing device;
(2) film that dull and stereotyped wire drawing device is formed oven dry is made removal of solvents, obtain polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane.
The present invention makes precursor polyamic acid (PAA) solution of polyimides (PI) as inner fluid, polyethylene glycol oxide (PEO) is as outer fluid, adopt coaxial electrostatic spinning technology, again by chemical imines method, PAA is made to be converted into PI, and then make polyimides as the sandwich layer composition firmly serving as the construction of cable mutually, mechanical stability and the thermomechanical stability of gel polymer electrolyte (GPE) membrane structure be made up of this polyimide fiber can be ensured; Make polyethylene glycol oxide as the soft shell sections serving as the construction of cable mutually, the advantage of polyethylene glycol oxide is that imbibition and water retainability are good, the pick up of pure PEO can reach more than 400%, owing to there is C-O-C key in molecular weight, usually there is compliance, associated matter can be formed, as the transmission channel of lithium ion with electron acceptor or some inorganic electrolyte.Therefore PEO is enclosed in the skin of PI as shell, the cable-type nanofiber of composition, not only have the advantage such as mechanical property and high-temperature stable method of PI, more have the advantage that imbibition and liquid-keeping property are strong, electrical conductivity is high of PEO concurrently, it is a kind of up-and-coming gel polymer electrolyte for lithium ion battery, and in the present invention, the solvent dissolving PEO is pure water, more meets the requirement of environmental protection.In addition, preparation method of the present invention is simple to operate, and reaction condition is gentle, and cost is low, good in economic efficiency.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the schematic diagram that the coaxial electrostatic spinning adopted according to the present invention prepares cable-type composite nano fiber;
Fig. 2 is the design sketch of cable-type composite nano fiber prepared in accordance with the present invention;
Fig. 3 is the scanning electron microscope (SEM) photograph of the cable-type composite nano fiber according to the embodiment of the present invention 1 preparation.
Description of reference numerals
1 second syringe 2 first syringe
3 high-pressure electrostatic 4 cable-type composite nano fibers
The dull and stereotyped wire drawing device of 5 ground connection
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein, this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is formed by the cable-type composite nano fiber containing polyimides sandwich layer and polyethylene glycol oxide cortex.
According to the present invention, with the gross weight of described cable-type composite nano fiber for benchmark, the content of described polyimides sandwich layer can be 20-80 % by weight, and the content of described polyethylene glycol oxide cortex can be 20-80 % by weight; Preferably, with the gross weight of described cable-type composite nano fiber for benchmark, the content of described polyimides sandwich layer can be 30-60 % by weight, and the content of described polyethylene glycol oxide cortex can be 40-70 % by weight.
According to the present invention, the diameter of described polyimides/polyethylene glycol oxide cable-type composite nano fiber can be 500-1000nm, be preferably 550-900nm, the external diameter of described polyimides sandwich layer can be 1:1.4-5 with the external diameter ratio of described polyethylene glycol oxide cortex, be preferably 1:1.4-3.5, the thickness of described polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane can be 10-30 μm, be preferably 17-22 μm, the porosity of described polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane can be 70-90%, pick up can be 500-800%, wherein, in the present invention, the external diameter of described polyimides sandwich layer refers to the overall diameter of described polyimides sandwich layer, and the external diameter of described polyethylene glycol oxide cortex refers to the overall diameter of the cortex of the donut-like of described polyethylene glycol oxide.
Present invention also offers the preparation method of a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein, the method comprises the following steps:
(1) polyamic acid/polyethylene glycol oxide cable-type composite nano fiber polyamic acid solution as inner fluid and the polyethylene oxide solutions as outer fluid prepared by coaxial electrostatic spinning silk device, and the polyamic acid of preparation/polyethylene glycol oxide cable-type composite nano fiber is collected on dull and stereotyped wire drawing device;
(2) film that dull and stereotyped wire drawing device is formed oven dry is made removal of solvents, obtain polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane.
According to the present invention, described polyamic acid solution can be prepared from for being dissolved in organic solvent by polyamic acid, described organic solvent can be N, N-dimethylacetylamide, N, one or more in dinethylformamide, 1-METHYLPYRROLIDONE, oxolane and dimethyl sulfoxide (DMSO), be preferably DMA.
According to the present invention, the concentration of described polyamic acid solution can be 10-30 % by weight, is preferably 15-20 % by weight.
According to the present invention, described polyethylene oxide solutions can be prepared from for being dissolved in deionized water by polyethylene glycol oxide, and wherein, described deionized water is not particularly limited, and preferably, described deionization electrical conductivity of water is 1 × 10
-14s/cm.
According to the present invention, the concentration of described polyethylene oxide solutions can be 10-30 % by weight, is preferably 15-20 % by weight.
According to the present invention, the consumption of described polyamic acid and described polyethylene glycol oxide makes the polyimides sandwich layer that can contain 20-80 % by weight in the gross weight of prepared polyimides/polyethylene glycol oxide cable-type composite nano fiber, polyimides sandwich layer preferably containing 30-60 % by weight, and the polyethylene glycol oxide cortex of 20-80 % by weight can be contained, the polyethylene glycol oxide cortex preferably containing 40-70 % by weight.
According to the present invention, first, on described dull and stereotyped wire drawing device, cable-type composite nano fiber is prepared by coaxial electrostatic spinning.The electrostatic spinning apparatus for coaxial electrostatic spinning in the present invention generally comprises high-pressure electrostatic, dull and stereotyped wire drawing device, the first syringe with the first boost motor for splendid attire inner fluid and the second syringe with the second boost motor for splendid attire outer fluid, wherein, for one end of first syringe with the first boost motor of splendid attire inner fluid with the inner core metal needle of 0.1-1mm, be preferably the inner core metal needle of 0.1-0.6mm, the other end can be the first boost motor, in like manner, for one end of second syringe with the second boost motor of splendid attire outer fluid with the outer cover metal syringe needle of 0.3-1.5mm, be preferably the outer cover metal syringe needle of 1-1.5mm, the other end can be the second boost motor, the positive pole of described high-pressure electrostatic is electrically connected with outer cover metal syringe needle and inner core metal needle, and the negative pole of described high-pressure electrostatic is electrically connected with dull and stereotyped wire drawing device.
According to the present invention, described dull and stereotyped wire drawing device is not particularly limited, as long as the conductive materials being easy to be formed film that can conduct electricity.
Fig. 1 shows the schematic diagram that the coaxial electrostatic spinning adopted according to the present invention prepares cable-type composite nano fiber; As shown in Figure 1:
This coaxial electrostatic spinning method comprises and respectively the polyamic acid solution as inner fluid and the polyethylene oxide solutions as outer fluid is placed in the first syringe and the second syringe, again the positive pole of high-pressure electrostatic is electrically connected with inner core metal needle and outer cover metal syringe needle respectively, negative pole is electrically connected with dull and stereotyped wire drawing device, open the supply voltage of high-pressure electrostatic and start coaxial electrostatic spinning silk device, like this, inner core metal needle in the first syringe and the second syringe and form high voltage electric field between outer cover metal syringe needle and dull and stereotyped wire drawing device, the polyamic acid solution as inner fluid in first syringe and the second syringe and the polyethylene oxide solutions as outer fluid are ejected by inner core metal needle and outer cover metal syringe needle and form unordered and/or orderly cable-type composite nano fiber, under the traction of electric field force, to be suspended in dull and stereotyped wire drawing device and in this dull and stereotyped wire drawing device, to form the cable-type composite nano-fiber membrane be made up of cable-type composite nano fiber, wherein, the condition of described coaxial electrostatic spinning comprises: the supply voltage of high-pressure electrostatic is 5-20kV, the fltting speed of the first boost motor is 0.2-1.6ml/h, be preferably 0.2-0.6ml/h, the fltting speed of the second boost motor is 0.2-1.6ml/h, be preferably 0.4-1ml/h, the internal diameter of inner core metal needle is 0.1-1mm, be preferably 0.1-0.6mm, the internal diameter of outer cover metal syringe needle is 0.3-1.5mm, be preferably 1-1.5mm, distance between described dull and stereotyped wire drawing device and inner core metal needle and outer cover metal syringe needle is 5-20cm.
And then the polyamic acid prepared through coaxial electrostatic spinning technology/polyethylene glycol oxide cable-type composite nano-fiber membrane oven dry is made removal of solvents, adopt chemical imines method, polyamic acid (PAA) is converted into polyimides (PI), obtains polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane; Wherein, the instrument of described oven dry adopts vacuum drying oven well-known to those skilled in the art, and the condition of described oven dry is not particularly limited, and preferably, the condition of described oven dry comprises: the temperature of oven dry can be 40-60 DEG C, and the time of oven dry can be 23-25 hour; More preferably, the temperature of oven dry can be 50 DEG C, and the time of oven dry can be 24 hours.
According to the present invention, after above-mentioned steps, prepared polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane can also be carried out mechanical stitch process, wherein, the condition of described mechanical stitch process comprises: pressure can be 5-10MPa, time can be 3-5 minute, and preferably, the time can be 3 minutes.
The design sketch of cable-type composite nano fiber prepared in accordance with the present invention as shown in Figure 2, in this Fig. 2, in the present invention, " soft phase A " represents the polyethylene oxide solutions as outer fluid, " soft phase B " represents the polyamic acid solution as inner fluid, and the two prepares cable-type composite nano fiber through coaxial electrostatic spinning, wherein, the cortex of the cable-type composite nano fiber prepared by letter " A " represents, the sandwich layer of the cable-type composite nano fiber prepared by letter " B " represents.
According to the present invention, environment temperature and the humidity of carrying out electrostatic spinning are not particularly limited, the temperature and humidity that can be well known to those skilled in the art, and preferably, carry out the environment temperature 25 DEG C of electrostatic spinning, humidity is 40%.
According to a kind of detailed description of the invention of the present invention, this preparation method specifically comprises the following steps:
(1) configuration is as the polyamic acid solution (sandwich layer solution) of inner fluid: be that the polyamic acid (PAA) of 10-30 % by weight is dissolved in preferred N by concentration, in N-dimethylacetylamide (DMAc), preferably can add a certain amount of imidization catalyst and dehydrating agent, load with the first boost motor for injecting in the syringe of inner fluid, stand-by;
(2) configuration is as the polyethylene oxide solutions (cortex solution) of outer fluid: be that the polyoxyethylene (PEO) of 10-30 % by weight is dissolved in deionized water by concentration, load with the second boost motor for injecting in the syringe of outer fluid, stand-by;
(3) consumption of polyamic acid and polyethylene glycol oxide is determined: the consumption of described polyamic acid and described polyethylene glycol oxide makes the polyimides sandwich layer containing 20-80 % by weight in the gross weight of prepared polyimides/polyethylene glycol oxide cable-type composite nano fiber, polyimides sandwich layer preferably containing 30-60 % by weight, and the polyethylene glycol oxide cortex containing 20-80 % by weight, the polyethylene glycol oxide cortex preferably containing 40-70 % by weight;
(4) select, inner core metal needle and outer cover metal syringe needle are installed, electrospinning parameters is set: the supply voltage of high-pressure electrostatic is 5-20kV, the fltting speed of the first boost motor is 0.2-1.6ml/h, be preferably 0.2-0.6ml/h, the fltting speed of the second boost motor is 0.2-1.6ml/h, be preferably 0.4-1ml/h, the internal diameter of inner core metal needle is 0.1-1mm, be preferably 0.1-0.6mm, the internal diameter of outer cover metal syringe needle is 0.3-1.5mm, be preferably 1-1.5mm, distance between described dull and stereotyped wire drawing device and inner core metal needle and outer cover metal syringe needle is 5-20cm,
(5) inner core metal needle and outer cover metal syringe needle are connected with the positive pole of high-pressure electrostatic, dull and stereotyped wire drawing device is connected with the negative pole of high-pressure electrostatic;
(6) on dull and stereotyped wire drawing device, collect the polyamic acid formed by the unordered and/or orderly cable-type composite nano fiber/polyethylene glycol oxide cable-type composite nano-fiber membrane of preparation;
(7) be dry process 23-25 hour in the baking oven of 40-60 DEG C in temperature by this polyamic acid/polyethylene glycol oxide cable-type composite nano-fiber membrane, make polyamic acid wherein be converted into polyimides by chemical imines method;
(8) this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is processed 3-5 minute under pressure is 5-10MPa.
Present invention also offers a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane prepared by said method, wherein, the diameter of described cable-type composite nano fiber is 500-1000nm, be preferably 550-900nm, the external diameter of described polyimides cortex and the external diameter of described polyethylene glycol oxide sandwich layer are than being 1:1.4-5, be preferably 1:1.4-3.5, the thickness of described polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is 10-30 μm, be preferably 17-22 μm, the porosity of described polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane can be 75-86%, pick up can be 480-720%.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples, polyimides is that the present inventor is made by oneself by the method for chemical imines PAA; Polyamic acid is purchased from Hangzhou Su Mengte Co., Ltd, and number-average molecular weight is 100,000; Polyethylene glycol oxide is purchased from acros organics, and number-average molecular weight is 150,000.
In the following Examples and Comparative Examples, high-voltage electrostatic spinning machine is purchased from Shenzhen concerted effort micro-nano Co., Ltd, and model is NEU011; ESEM is purchased from Japanese JEOL, and model is JSM-7600FE.
In the following Examples and Comparative Examples, the pick up of this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is tested: (lithium salts is LiPF6 to be immersed in electrolyte after weighing up the quality of this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane, concentration is 1mol/L, solvent is EC, EMC, DEC, mass concentration ratio is 2:3:1) middle 24h, then taking-up filter paper blots the liquid on this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane surface, obtain corresponding gel polymer electrolyte, weigh the quality of the gel polymer electrolyte of now this correspondence, operation is all carried out in the glove box being full of argon gas.According to formulae discovery: pick up %=(Wi-W)/W × 100%;
Wherein, W is the quality of dry film; Wi is the quality after dry film has soaked 24h in the electrolytic solution.
In the following Examples and Comparative Examples, to this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane (W
d) porosity test: take out after the polyimides of having weighed/polyethylene glycol oxide cable-type composite nano-fiber membrane soaks 2h in n-butanol, blot gently with the liquid of filter paper by its surface, then carry out weighing (W
w), can obtain nano fibrous membrane absorb the quality W of n-butanol
b=W
w-W
d. the pore volume of nano fibrous membrane can by the quality (W of n-butanol
b) with the density (ρ of n-butanol
b) being divided by obtains, this volume is the porosity P%=(W of nano fibrous membrane with the ratio of dry film volume
w-W
d)/(ρ
bv
p).
In the following Examples and Comparative Examples, the electrical conductivity of this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is tested: this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is placed between two stainless steel substrates, (lithium salts is LiPF6 to the electrolyte of absorption q.s, concentration is 1M/L, solvent is EC, EMC, DEC, mass concentration ratio is 2:3:1), obtain corresponding gel polymer electrolyte, after being sealed in 2016 type button cells, carry out AC impedance experiment, intersection point that is linear and real axis is the bulk resistance of gel polymer electrolyte, the ionic conductivity obtaining gel polymer electrolyte thus can according to formulae discovery:
Conductivityσ=L/ (AR),
Wherein, L represents the thickness of gel polymer electrolyte, and A is the contact area of corrosion resistant plate and film, and R is the bulk resistance of polymer dielectric.
Embodiment 1
(1) using dissolved for PAA be 98% concentration in purity be as sandwich layer solution in the DMA of 15 % by weight, load in the first syringe of coaxial electrostatic spinning silk device; PEO to be dissolved in concentration be 15 % by weight electrical conductivity is 1 × 10
-14in the deionized water of S/cm, load in the second syringe of coaxial electrostatic spinning silk device;
(2) coaxial electrostatic spinning condition (except fltting speed) arranges as follows: the supply voltage of high-pressure electrostatic is 20kV, the internal diameter of inner core metal needle is 0.8mm, the internal diameter of outer cover metal syringe needle is 1.2mm, distance between described dull and stereotyped wire drawing device and inner core metal needle and outer cover metal syringe needle is 15cm, the environment temperature of carrying out electrostatic spinning is 25 DEG C, humidity is that the fltting speed of 40%, PAA and PEO is respectively 0.2ml/h and 0.8ml/h.
(3) spinning terminated after 6 hours, took off film, adopt chemical imines method in an oven temperature be at 50 DEG C dry 24 hours, PAA is converted into PI, and adopts the pressure of 10MPa to its roll extrusion 3 minutes.
Result obtains polyimides/polyethylene glycol oxide cable-type composite nano fiber that thickness is 17 μm, as the scanning electron microscope (SEM) photograph of cable-type composite nano fiber prepared as can be seen from Fig. 3 embodiment 1, the diameter of polyimides prepared by the present invention/polyethylene glycol oxide cable-type composite nano fiber is about 550nm, and its center core layer diameter is about about 130nm.
The TENSILE STRENGTH of testing this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is 34MPa, and porosity is 86%, and the pick up of corresponding gel polymer electrolyte is 720%, and electrical conductivity is 2.0 × 10
-3s/cm.
Embodiment 2
(1) using dissolved for PAA in purity to be 98% concentration the be DMA of 20 % by weight as sandwich layer solution, load in the first syringe of coaxial electrostatic spinning silk device; PEO is dissolved in concentration be 15 % by weight electrical conductivity be 1 × 10
-14in the deionized water of S/cm, load in the second syringe of electrostatic spinning apparatus;
(2) coaxial electrostatic spinning condition (except fltting speed) arranges as follows: the supply voltage of high-pressure electrostatic is 20kV, the internal diameter of inner core metal needle is 0.8mm, the internal diameter of outer cover metal syringe needle is 1.2mm, distance between described dull and stereotyped wire drawing device and inner core metal needle and outer cover metal syringe needle is 18cm, the environment temperature of carrying out electrostatic spinning is 25 DEG C, humidity is that the fltting speed of 40%, PAA and PEO is respectively 0.3ml/h and 1.0ml/h;
(3) spinning terminated after 6 hours, took off film, adopt chemical imines method in an oven temperature be at 50 DEG C dry 24 hours, PAA is converted into PI, and adopts the pressure of 10MPa to its roll extrusion 3 minutes.
Result obtains polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane that thickness is 22 μm.
Through detecting, the diameter of this polyimides/polyethylene glycol oxide cable-type composite nano fiber is about 700nm, and its center core layer diameter is about about 190nm.
The TENSILE STRENGTH of testing this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is 38MPa, and porosity is 81%, and the pick up of corresponding gel polymer electrolyte is 680%, and electrical conductivity is 1.7 × 10
-3s/cm.
Embodiment 3
(1) using dissolved for PAA in purity to be 98% concentration the be DMA of 15 % by weight as sandwich layer solution, load in the first syringe of electrostatic spinning apparatus; PEO to be dissolved in concentration be 20 % by weight electrical conductivity is 1 × 10
-14in the deionized water of S/cm, load in the second syringe of electrostatic spinning apparatus;
(2) coaxial electrostatic spinning condition (except fltting speed) arranges as follows: the supply voltage of high-pressure electrostatic is 20kV, the internal diameter of inner core metal needle is 0.8mm, the internal diameter of outer cover metal syringe needle is 1.2mm, distance between described dull and stereotyped wire drawing device and inner core metal needle and outer cover metal syringe needle is 15cm, the environment temperature of carrying out electrostatic spinning is 30 DEG C, humidity is that the fltting speed of 20%, PAA and PEO is respectively 0.5ml/h and 0.5ml/h;
(3) spinning terminated after 6 hours, took off film, adopt chemical imines method in an oven temperature be at 50 DEG C dry 24 hours, PAA is converted into PI, and adopts the pressure of 15MPa to its roll extrusion 3 minutes.
Result obtains polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane that thickness is 18 μm.
Through detecting, the diameter of this polyimides/polyethylene glycol oxide cable-type composite nano fiber is about 770nm, and its center core layer diameter is about about 320nm.
The TENSILE STRENGTH of testing this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is 47MPa, and porosity is 79%, and the pick up of corresponding gel polymer electrolyte is 645%, and electrical conductivity is 1.3 × 10
-3s/cm.
Embodiment 4
(1) using PAA dissolved in concentration be the DMA of 20 % by weight as sandwich layer solution, load in the first syringe of electrostatic spinning apparatus; PEO to be dissolved in electrical conductivity be concentration be 20 % by weight 1 × 10
-14in the deionized water of S/cm, load in the second syringe of electrostatic spinning apparatus;
(2) coaxial electrostatic spinning condition (except fltting speed) arranges as follows: the supply voltage of high-pressure electrostatic is 20kV, the internal diameter of inner core metal needle is 0.8mm, the internal diameter of outer cover metal syringe needle is 1.2mm, distance between described dull and stereotyped wire drawing device and inner core metal needle and outer cover metal syringe needle is 10cm, the environment temperature of carrying out electrostatic spinning is 25 DEG C, humidity is that the fltting speed of 40%, PAA and PEO is respectively 0.6ml/h and 0.4ml/h;
(3) spinning terminated after 6 hours, took off film, adopt chemical imines method in an oven temperature be at 50 DEG C dry 24 hours, PAA is converted into PI, and adopts the pressure of 10MPa to its roll extrusion 3 minutes.
Result obtains polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane that thickness is 17 μm.
Through detecting, the diameter of this polyimides/polyethylene glycol oxide cable-type composite nano fiber is about 900nm, and its center core layer diameter is about about 570nm;
The TENSILE STRENGTH of testing this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is 53MPa, and porosity is 75%, and the pick up of corresponding gel polymer electrolyte is 480%, and electrical conductivity is 1.1 × 10
-3s/cm.
Comparative example 1
Prepare polyimides/Kynoar cable-type composite nano-fiber membrane according to the method identical with embodiment 1, institute's difference is, the polyethylene glycol oxide in embodiment 1 is replaced with the Kynoar (PVDF) that molecular weight is 60.
Result obtains polyimides/Kynoar cable-type composite nano-fiber membrane film that thickness is 17 μm.
Through detecting, the diameter of this polyimides/Kynoar cable-type composite nano fiber is about 900nm, and its center core layer diameter is about about 810nm.
The TENSILE STRENGTH of testing this polyimides/Kynoar cable-type composite nano-fiber membrane is 30MPa, and porosity is 76%, and the pick up of corresponding gel polymer electrolyte is 43%, and electrical conductivity is 1.9 × 10
-4s/cm.
Result as can be seen from above-described embodiment 1-4 and comparative example 1: pick up and the electrical conductivity of the gel polymer electrolyte that sandwich layer diameter is little, TENSILE STRENGTH is high, corresponding of polyimides/Kynoar cable-type composite nano-fiber membrane that the polyimides adopting method of the present invention to prepare/polyethylene glycol oxide cable-type composite nano-fiber membrane is prepared relative to comparative example significantly improve.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane, is characterized in that, this polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is formed by the cable-type composite nano fiber containing polyimides sandwich layer and polyethylene glycol oxide cortex.
2. polyimides according to claim 1/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein, with the gross weight of described cable-type composite nano fiber for benchmark, the content of described polyimides sandwich layer is 20-80 % by weight, be preferably 30-60 % by weight, the content of described polyethylene glycol oxide cortex is 20-80 % by weight, is preferably 40-70 % by weight.
3. polyimides according to claim 1/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein, the diameter of described cable-type composite nano fiber is 500-1000nm, be preferably 550-900nm, the external diameter of described polyimides sandwich layer and the external diameter of described polyethylene glycol oxide cortex are than being 1:1.4-5, be preferably 1:1.4-3.5, the thickness of described polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is 10-30 μm, be preferably 17-22 μm, the porosity of described polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is 75-86%, pick up is 480-720%.
4. a preparation method for polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane, it is characterized in that, the method comprises the following steps:
(1) polyamic acid solution as inner fluid and the polyethylene oxide solutions as outer fluid are prepared polyamic acid/polyethylene glycol oxide cable-type composite nano fiber by coaxial electrostatic spinning silk device, and the polyamic acid of preparation/polyethylene glycol oxide cable-type composite nano fiber is collected on dull and stereotyped wire drawing device;
(2) film that dull and stereotyped wire drawing device is formed oven dry is made removal of solvents, obtain polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane.
5. method according to claim 4, wherein, described polyamic acid solution is prepared from for being dissolved in organic solvent by polyamic acid, described organic solvent is N, N-dimethylacetylamide, N, one or more in dinethylformamide, 1-METHYLPYRROLIDONE, oxolane and dimethyl sulfoxide (DMSO), are preferably DMA.
6. method according to claim 4, wherein, described polyethylene oxide solutions is prepared from for being dissolved in deionized water by polyethylene glycol oxide.
7. according to the method in claim 4-6 described in any one, wherein, the concentration of described polyamic acid solution is 10-30 % by weight, is preferably 15-20 % by weight; The concentration of described polyethylene oxide solutions is 10-30 % by weight, is preferably 15-20 % by weight.
8. method according to claim 7, wherein, the consumption of described polyamic acid and described polyethylene glycol oxide makes the polyimides sandwich layer containing 20-80 % by weight in the gross weight of prepared polyimides/polyethylene glycol oxide cable-type composite nano fiber, polyimides sandwich layer preferably containing 30-60 % by weight, and the polyethylene glycol oxide cortex containing 20-80 % by weight, the polyethylene glycol oxide cortex preferably containing 40-70 % by weight.
9. method according to claim 4, wherein, in step (1), described coaxial electrostatic spinning silk device comprises high voltage source, with the syringe for injecting inner fluid of the first boost motor, with the syringe for injecting outer fluid of the second boost motor, inner core metal needle, outer cover metal syringe needle and dull and stereotyped wire drawing device, wherein, the condition of coaxial electrostatic spinning comprises: high-voltage power voltage is 5-20kV, the fltting speed of the first boost motor is 0.2-1.6ml/h, be preferably 0.2-0.6ml/h, the fltting speed of the second boost motor is 0.2-1.6ml/h, be preferably 0.4-1ml/h, the internal diameter of inner core metal needle is 0.1-1mm, be preferably 0.1-0.6mm, the internal diameter of outer cover metal syringe needle is 0.3-1.5mm, be preferably 1-1.5mm, distance between described dull and stereotyped wire drawing device and inner core metal needle and outer cover metal syringe needle is 5-20cm.
10. method according to claim 4, wherein, in step (2), the condition of described oven dry comprises: the temperature of oven dry is 40-60 DEG C, and the time of oven dry is 23-25 hour.
11. methods according to claim 4, wherein, the method also comprises polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane step (2) prepared and carries out mechanical stitch process.
12. methods according to claim 11, wherein, the condition of described mechanical stitch process comprises: pressure is 5-10MPa, and the time is 3-5 minute.
13. polyimides prepared by the method described in claim 4-12 any one/polyethylene glycol oxide cable-type composite nano-fiber membrane.
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